Reclaiming dry batteries



, UNITED STATES rarest-orator.-

GARLETON ELLIS AND ALFRED A. WELLS, or MONTCLAIR, NEW masnxnssrenon's, BY MESNE ASSIGNMENTS, TO NATIONAL oAnBoNcoMrANY, Inc on NEW YORK,

N. Y., A CORPORATION OF NEW- YORK.

RECLAIMING DRY BATTERIES.

No Drawing. Application filed September 29,1917, Serial No. 194,072. Renewed June 14, .1920. Serial Specification of Letters Patent.

Patented A t. 5, 1921.

To all wiwm'z't may concern:

Be it known that we, .OARLETON ELLIS and ALFRED A.- l VELLS,. citizens of the United States, and residents of Montclair, in the county of Essex and State of New Jersey,

have invented certain new and useful Im provements in Reclaiming Dry Batteries, of which the following is a specification. V p

This invention relates to a method of reclaiming dry batteries of the Leclanche type.

and involves two modifications, one, direct chemical treatment, and the other, heat treatment, followed or not, as the case may be, by chemical treatment. 1 v

The ordinary dry battery has a comparatively short life due to the fact that the solution which it contains is relatively quickly exhausted. Oftentimes this happens long before any very. material con' sumption'of the zinc element has occurred.

Sometimes, in fact, the voltage of the bat tery will fall rapidly so that the battery becomes useless, in an automobile for instance, for I p the battery is discarded. Such a battery contains a considerable amount of zinc, with brass binding posts, carbon pencil, a mixture of graphite and' manganese dioxid as depolarizing .mater-ial, salts such-as ammonium chlorid and zinc chloridand a sealing mass of pitch By the present process all these materials may belrecovered to a greater or less degree.

By the chemical treatment, for example, the used cell may be placed in a reagent such as acid, or preferably in a solution containing from '10 to 20% .more or less of sodium bisulfate or Sodium acid sulfate, such as niter cake and similar acid salts, which form a by-produot in the manufacture of acids. Caustic soda may be employed-in some cases as the reagent. A solution of'sodiumbi sulfate, which may be heated if desired, dissolves the zinc container, leaving the solder intact, which may be collected; The brass binding and when not greatly affected by exposure ered.

depolarizing mass is then removed and the operating an ignition system and I a solution of sulfuric or hydro-chloric posts may. or may not be 'attaclred according. to the conditions of operation,

depolarizing mass preferably separated from the carbon rod. The latter may be washed or boiled in water or dilute acid to" free, from salts and maybe used again. The graphite and manganese dioxid be'washed to remove zinc chlorid, "ammonia and ammonium salts or any soluble manganese "salts and the insoluble material may' an oxldlzing agent such as be treated with sodium hypochlorite orchlorin in water at the boiling and similar agent to raise the degree of oxidation to the dioxid condition to a suflicient extent "so that themass may again'be used fondepolarizingpurposes. In some cases if considerable manganese material is pres may point, potassium permanganate ent in a Soluble form, the depolarizing mass without washing,

may be treated with the oxidizlng agent to precipitate manganesefrom the soluble salts and also to secure oxidation of the lower oxids of manganeseor insoluble v, manganese higher 'oxids, for; "depolarizing purposes.

chlorid and ammonium be separated and refined, if desired. The pitch which is customarilyi'used to sealfthe topofthe container is of course, preferably removed before these operations are con-, ducted i Dry batteries are found two forms, the ordinary size used for electric bell purposes, 3

are thus present in a form capable of ex} traction by mixing with dilute acid or some similar procedure to form a manganese solu-v customary to I use bodies to formthe V he mass may betreated to removei zinc' salts and these tion which may be subsequently oxidized by treatment with an oxidizing agent such as by boilingwithsodium ilar procedure to yield hypochloriteor simhydrated manganese i 95. to a compound or compounds of the loweroxide or to the lower oxids themselves and especially if a pure hydrate is prepared. In

" pounds which are dioxid, for. example, deep black hydrated manganese dioxid, useful in the manufacture of depolarizing mixtures for minlature cells,

this way theoperation of the large sizedry battery containing mineral manganese serves to produce a lower form of manganese capable of reoxidation to the hydrated form for use in the more expensive miniature cells. In a similar manner the manganese compounds may beconverted into the, nitrate for example, and roasted man or oxygen to form manganese dioxid. This may be done in the presence of the graphite if desired. If roasting does not completely oxidize to manganese dioxid, av further treat-v ment of the mass may be carried: out with potassium permanganate. The roasting should be carried out under temperature conditions to produce the dioxi d without heat-' ingto a point where too dense a material would be secured for satisfactory use in min iature batteries. Of course, if the material is used in the large size batteries, there-is not the need of such care in the oxidation by roasting. The zinc salts or basic zinc comobtained may be sold such or may be reduced to the metallic condition if desired. Thus the products obtainedmay beemployed to reconstruct new batteries or may be used in the arts in different ways according'to local conditions. The second modification of the process contemplates a thermal. treatment which preferably involves heating of the battery to temperatures graduated tomake a separation-of some of the components of the battery in a cheap and eiiicientmanner: To this end the battery or. batteries may be placed in a mufiie furnace and heated until the pitch-is softened and is collected and removed. The temperature is' gradually raised until the solder softens and the zine covering may be stripped from .thebattery 7 paper lining I by hand or by mechanical device, as for example, by agitating in a tumbler. The which is in contact with the zinc, also usually readly comes 01f under these conditions. While hot, the depolarizing mass separates with considerable ease from the carbon pencil, hence the depolarizing agentmay be readilyflremoved and the carbon pencil recovered, which may be washed and reused. Any fumes of ammonium chloridor amrnonia vapors produced during the operation may be collected. Or-

dinarily the temperature may be kept below the point at which ammonium ,chlorid sublimes. The depolarizing mass be ex tracted with water toremove the. soluble .salts which are collected and the zinc salts separated frointheammoniuni salts, or-man- 1 ganese salts, ifpresent. For example, if it. contains the manganese salt, the solution may be treated by boiling with hypochlorite to produce manganesedioxid which is col- 7 by a special machine and the zinc removed in a mechanical way. It is also possible to apply the same procedure to soldered conainers.

Considering, for sake of illustration, the

ordinary soldered container, an apparatus may be arranged involving mechanical appliances for [passing the spent batteries through a furnaceor heated chamber so as to allow the pitch to runoff and then to melt the solderq The batteries are then placed in a tumbler and shaken or rattled, thereby removing the zinc container and bibulo-us paper, and separating the carbon pencils from' the depolarizing agent. The latter usually breaks up into a powder. A oer tain amount of the depolarizing agent may' cling somewhat tenaciously, to the paper however. The depolarizing agent passes through screens and the mixture of sheet zinc, carbon pencils and paper liriings is conveyed to a point, wherethe separation. of

these materials may be made mechanically or byha'nd as desired. The zinc sheets are collected and may be melted. The. carbon pencils, as stated, may be washed and re-- used. If some of them are considerably abraided by the tumbling action, these may be ground up, and may find application in admixture with manganese dioxid for depolarizing purposes. The bibulous paper contains a certain amount of soluble andjin soluble'salts or basic bodies and also some adhering depolarizing agent. As a rule the former may be extracted by boiling with?- water or dilute acid and the salts recovered and separated if desired. In casethe ,depolarizing agent cannot be readily removed otherwise, the paper may be ignited and the, depolarizing agent thus separated and purified as maybe desired. The. depolarizing,

mass obtained from the tumbler may be extracted with water or diluteaci'd to get out; the soluble, salts. 'Any'zinc or ammonium salt present may be duly separated fromthe manganese salts. Manganese dioxid may be prepared, such for example,"as deep black good conducting manganese dioxid, used in miniature dry batteries. The spentfdepo- 1- larizing, agent. may be oxidized, if desired, 1

by roasting or treatment with an oxidizing agent such as hypochlorite, in some cases followed by treatment with potassium permanganate to oxidize any residual lower oxidsof manganese. If desired, in view of the fact thatthe discharge of a battery conzinc container of the taining mineral manganese dioxid produces a lower form of manganese oxid or salt, the spent depolarizing mass may be extracted with hydrochloric, sulfuric or nitric acid and the like, to get a lower form of manganese .dioxid which may be suitably o-xidized to form the'artificial hydrated product or may be roastedto .form anhydrous manganese dioxld or manganite as the case may be; In fact, in referring tothe production as a fairly resistant compound into one easily attackabl e by acids, thereby enabling the simple production of manganese salts from what has heretofore been a waste product or waste material.

When the zinc element of the battery has been eaten or corroded to such an extent that a good deal-of the zinc is in a very thin or flaky form the separation of the metal should be carried out with due consideration for these conditions. The upper part of the battery is less likely to be attacked during the operation of the battery than the lower part, hence the upper portion containingthe usual brass con-* nections or binding posts sometimes may be separated from the rest of the material in an advantageousmanner.

Many of the spent batteries when opened give off the odor of ammonia and from the contents may be extracted a white flaky precipitated material readily soluble in hydrochloric acid and being a hydrate of zinc or a basic compound of zinc. This material may be separated and the content of zinc utilized as desired.

lVhat we claim is 1. The process of reclaiming spent batteries of the Leclanche type which comprises heating the battery to a temperature to melt the pitch and soften the solder, in

1 stripping the zinc sheet from the carbon and depolarizing element, in separating the carbon element, and in reviving the depolarizing material. v

2. The process of reclaiming spent dry batteries of the Leclanche type which comprises heating the battery to a temperature to soften the solder, in removing the zinc sheet from the depolarizing element and in separating the carbon element.

the zinc remains intact and in I removing the zinc 1n the formof sheets or dry 3. In the process of l reclaimingspent batteries of the Leclanche type, the step which comprises agitating thecarbon pencil and adhering whereby the latter pencil.

4:.In the process of batteries of theLeclanche type, the step Which comprises agitating the carbon pendepolarizing material,

is separated 1 from the reclaimlng spent cil and adhering depolarizing material in a heated state, whereby rated from-the pencil.- 5. "In 7 'the process of the latter is sepacil from adhering depolarizing material.

6. The process of teries of the Leclanche type, which comprises removing the metal container and separatin at least some of the component parts of the contents of said container.

7 In the process of recovering or rereclaiming spent; batteries of theLeclanche. type, -the step which comprises stripping the carbon penreclaiming spent batclaiming spent batteries of the Leclanche type, the step which comprises treating the spent depolarizing material with an oxidizing agentto reoxidize the manganese material.

8. In the process of recovering or reclaiming spent batteries of the Leclanche type,jthe step which comprises treating the spent depolarizing'material admixed with graphite with an oxidizing agent to reoxidize the manganese material.

9. Inthe process of recovering or reclaiming spent batteries of the Leclanche type, the step which comprises treating the spent depolarizing material withan oxidizing agent.

.10.'In the process of reclaiming spent batteries of the Leclanche type, the step which comprises heating the batteries to a temperature at which the solder melts but subsequently depolarizing material the water soluble saltsv which are present. I

14. In the recovery from spent batteries of the materials used in the manufacture of dry batteries of the Leclanche type, the

the solder melts and step which comprises separating, thespent depolarizing agent, in acting on it With a reagent to dissolve manganese compounds, and in oxidizing the manganese solution so obtained to produce a higher oxid of man-- ganese. Y

.15., In the recovery from spent batteries of the materials used in the manufacture of dry batteries of: the Leclanche type, the

step Which comprises separating the spent depolarizing agent consisting of manganese material and carbon, 1n, actlng on it with a reagent to dissolve manganese compounds,

and in oxidizing the manganese solution so obtainedv to produce alhigher oxid of" manganese.

' 16. In the recovery from spentbatteries of the materials used in the manufacture of dry batteries of the Leclanche type, the,

ganese. Y. 7

- GARLETON ELLIS.

, .ALFRED A; WELLS. 

